WO1996037484A1 - Process for producing 5,6-dihydro-1,3-oxazines - Google Patents

Process for producing 5,6-dihydro-1,3-oxazines Download PDF

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Publication number
WO1996037484A1
WO1996037484A1 PCT/EP1996/001954 EP9601954W WO9637484A1 WO 1996037484 A1 WO1996037484 A1 WO 1996037484A1 EP 9601954 W EP9601954 W EP 9601954W WO 9637484 A1 WO9637484 A1 WO 9637484A1
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Prior art keywords
alkyl
formula
substituted
alkoxy
phenyl
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PCT/EP1996/001954
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German (de)
French (fr)
Inventor
Bernd Alig
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Bayer Aktiengesellschaft
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Priority to BR9609218A priority Critical patent/BR9609218A/en
Priority to EP96914186A priority patent/EP0827499B1/en
Priority to AU57640/96A priority patent/AU5764096A/en
Priority to JP8535306A priority patent/JPH11505261A/en
Priority to US08/930,051 priority patent/US5892030A/en
Priority to DE59611076T priority patent/DE59611076D1/en
Publication of WO1996037484A1 publication Critical patent/WO1996037484A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • the invention relates to a new process for the preparation of partially known 5,6-dihydro-1,3-oxazines, new 5,6-dihydro-1,3-oxazines, as well as new intermediates for their preparation and their use for controlling animal pests.
  • A stands for substituted phenyl or for optionally substituted naphthyl, pyridyl, thienyl or pyrazolyl and
  • B for hydrogen, alkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, optionally substituted cycloalkyl or in each case optionally substituted phenyl, phenylalkyl, phenylalkenyl, phenoxyalkyl, phenylthioalkyl,
  • R 1 and R 2 are the same or different and each represents alkyl or
  • 5,6-dihydro-1,3-oxazines of the formula (I) can be obtained in good yields and in high purity by the process according to the invention, although no noticeable reaction was to be expected due to the low reactivity of the ethylene.
  • the implementation according to the invention thus has the advantage of a more cost-effective process implementation with simultaneous improvement in yield, in particular with regard to the overall process, i.e. including the manufacture of the product (see also the manufacturing examples).
  • A preferably represents phenyl which is monosubstituted to pentasubstituted by identical or different halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 - alkylthio, C 1 -C 6 haloalkyl , C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkylthio, nitro, cyano or by optionally single to fivefold, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl , C 1 -C 6 - Alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio substituted phenyl, for optionally mono- to triple, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or C 1 -
  • C 1 -C 6 alkyl preferably represents hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, C 1 -C 6 -Halogenalkyl or C 2 -C 6 -alkenyl, for optionally single to fivefold, identical or different by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkyl or C 1 - C 6 -C haloalkoxy substituted C 3 -C 7 cycloalkyl, for optionally single to triple, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl , C 1 -C 6 haloalkoxy or cyano substituted pyridyl, for each
  • Phenyl ring substituted phenyl, benzyl, pheneth-1-yl, pheneth-2-yl, phen oxymethyl, phenylthiomethyl, phenylthioeth-1-yl, phenoxyeth-1-yl, phenoxyeth-2-yl or styryl, where in each case are suitable as substituents
  • Phenyl-substituted cyclohexyl or cyclohexyloxy optionally mono- or disubstituted, identically or differently by halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl-substituted pyridyloxy, in each case optionally mono- to quintuple, identically or differently by halogen, C 1 - C 12 alkyl, C 1 -C 4 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 - C 6 alkoxy ethyleneoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio substituted phenyl, phenyl C 1 -C 6 alkyl, phenoxy, phenylthio, phenyl C 1 -
  • Chlorine, bromine, methyl or ethyl-substituted thienyl or pyrazolyl which is optionally monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine or C 1 -C 3 -alkyl.
  • Alkenyl for each optionally single to triple, identical or different, fluorine, chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, CF 3 or OCF 3 substituted cyclopropyl, cyclopentyl or cyclohexyl, for optionally single or twice, the same or different
  • each cyclohexyl or cyclohexyloxy optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclohexyl or phenyl,
  • B very particularly preferably represents hydrogen, C 1 -C 4 alkyl, C 1 -C 2 -
  • Pyridyl for each optionally mono- or disubstituted, identically or differently, by fluorine, chlorine, CH 3 or C 2 H 5, ⁇ -pyrrolyl or ⁇ -pyrrolyl, by CHO, hydroxy, cyano, carboxyl, di-C 1 -C 6 alkoxy-C 1 -C 4 -alkyl or C 1 -C 8 -alkoxycarbonyl-substituted phenyl or for phenyl, benzyl, pheneth-1-yl, pheneth-2-yl which are optionally monosubstituted to trisubstituted identically or differently in the phenyl ring, Phenoxymethyl, phenylthiomethyl, phenylthioeth-1-yl, phenoxyeth-1-yl, phenoxyeth-2-yl, or styryl, where in each case are suitable as substituents
  • each cyclohexyl or cyclohexyloxy optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclohexyl or phenyl,
  • Preferred compounds which can be prepared according to the invention are substances of the formula (Ia)
  • A stands for the general, preferred, particularly preferred and very particularly preferred meanings mentioned above and B 1 represents mono- to pentasubstituted, identically or differently substituted phenyl, the substituents which may be mentioned as preferred, particularly preferred and very particularly preferred substituents under B for the phenyl radical.
  • a particularly preferred group of substances which can be prepared according to the invention are compounds of the formula (I)
  • A represents phenyl substituted once or twice, identically or differently by fluorine or chlorine, and
  • Formula (II) provides a general definition of the amide derivatives to be used as starting materials in the process according to the invention.
  • a and B preferably or in particular have those meanings which have already been given as preferred, particularly preferred or very particularly preferred for A and B in connection with the description of the compounds of the formula (I) which can be prepared according to the invention .
  • R 1 and R 2 are the same or different and are preferably C 1 -C 4 -
  • Alkyl in particular for methyl, ethyl, n- or i-propyl or preferably together with the N atom to which they are attached, for a 5- or 6-membered group which is optionally monosubstituted to pentasubstituted, preferably monosubstituted or disubstituted, in the same or different manner Heterocycle, optionally one or two more
  • Heteroatoms preferably a further heteroatom, such as O, S or NR, may be mentioned as substituents, in particular C 1 -C 4 alkyl and C 1 -C 4 alkoxy and where R is alkyl, preferably C 1 -C 4 - Alkyl, or optionally substituted aryl, in particular optionally optionally mono- or disubstituted, identically or differently substituted phenyl, where the following may be mentioned as preferred substituents: halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 - C 4 - alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio and C 1 -C 4 - haloalkylthio.
  • substituents in particular C 1 -C 4 alkyl and C 1 -C 4 alkoxy and where R is alkyl, preferably C 1 -C 4 - Alkyl, or
  • B 2 has the meaning given for B with the exception of hydrogen.
  • amide derivatives of the formula (Ila) are obtained, for example, by amides of the formula (III) A-CO-NH 2 (III) in which
  • R 1 and R 2 have the meaning given above, if appropriate in the presence of a diluent.
  • amides of the formula (III), aldehydes of the formula (IV) and secondary amines of the formula (V) required as starting materials for the preparation of the amide derivatives of the formula (II) are generally known or can be obtained in a generally known manner.
  • Suitable diluents for carrying out the process for the preparation of the amide derivatives of the formula (II) are all inert organic solvents which are customary for such reactions.
  • Alcohols such as methanol or ethanol can preferably be used;
  • Esters such as methyl acetate or
  • Ethers such as diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, and also nitriles, such as acetonitrile; also optionally halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, hexane, cyclohexane, benzene, toluene, xylene or chlorobenzene; such as
  • reaction temperatures can be varied within a substantial range when carrying out the process for the preparation of the amide derivatives of the formula (II). In general, temperatures between 0 and 120 ° C, preferably between 10 and 100 ° C. When carrying out the process for the preparation of the amide derivatives
  • Formula (II) is generally employed per mole of amide of formula (III) 1.0 to 1.5 moles, preferably 1.0 to 1.2 moles of aldehyde of formula (IV) and 1.0 to 2.0 moles , preferably 1.0 to 1.2 mol of secondary amine of the formula (V).
  • reaction is carried out, worked up and isolated according to generally customary methods.
  • the amide derivatives of formula (II) can optionally also be directly, i.e. without being isolated, are reacted with ethylene to give the end products of the formula (I) in the process according to the invention (cf. also the preparation examples).
  • the new amide derivatives of the formula (Ila) also show good biological effects when used to control animal pests.
  • the process according to the invention for the preparation of the compounds of the formula (I) is carried out in the presence of hydrogen chloride gas and a catalyst.
  • Lewis acids preferably transition metal halides, in particular titanium tetrachloride, tin tetrachloride and zinc dichloride are suitable as catalysts.
  • the process according to the invention is preferably carried out in the presence of a diluent.
  • Suitable diluents are conventional organic solvents, e.g. optionally halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons. These include, for example, chlorobenzene, dichlorobenzene,
  • Petroleum ether, hexane, cyclohexane, dichloromethane, chloroform and carbon tetrachloride Petroleum ether, hexane, cyclohexane, dichloromethane, chloroform and carbon tetrachloride.
  • reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. Generally works one at temperatures between -120 ° C and + 120 ° C, preferably at temperatures between 10 ° C and 100 ° C.
  • the workup can be carried out in the usual way; the reaction mixture is preferably made alkaline with cooling at temperatures between 0 ° C. and 10 ° C. and the end product is isolated in a generally customary manner.
  • the 5,6-dihydro-1,3-oxazines of the formula (I) to be prepared by the process according to the invention are largely known (cf., for example, EP-A 0 635 500 and WO-A 94/14783) and are used to control animal pests used.
  • A has the meaning given above and D for each optionally substituted 2- or 3-pyrrolyl or for by
  • the compounds of the formula (Ib) can also be present as geometric and / or optical isomers or isomer mixtures of different compositions, depending on the nature of the substituents.
  • the invention relates to both the pure isomers and the isomer mixtures.
  • the compounds of the formula (Ib) according to the invention show a considerably better activity against animal pests than the most similar known compounds in terms of constitution.
  • the compounds of the invention are generally defined by the formula (Ib).
  • A preferably represents phenyl which is monosubstituted to pentasubstituted by identical or different halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 - alkylthio, C 1 -C 6 haloalkyl , C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkylthio, nitro, cyano or by optionally single to fivefold, identical or different by halogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl , C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio substituted phenyl, for optionally mono- to trisubstituted, identically or differently substitute
  • D preferably represents 2-pyrrolyl or 3-pyrrolyl, optionally substituted once or twice, identically or differently by halogen or C 1 -C 4 alkyl, or by CHO, cyano, carboxyl, poly-C 1 -C 8 alkoxy -C 1 -C 8 alkyl or C 1 -C 8 alkoxycarbonyl substituted phenyl.
  • Chlorine, bromine, methyl, ethyl or pyrazolyl which is optionally monosubstituted to trisubstituted identically or differently, where substituents are mentioned
  • D particularly preferably represents 2-pyrrolyl or 3-pyrrolyl optionally substituted once or twice, identically or differently, by fluorine, chlorine or C 1 -C 3 -alkyl, or by CHO, cyano, carboxyl, poly-C 1 -C 8- alkoxy-C 1 -C 6 alkyl or C 1 -C 8 alkoxycarbonyl substituted phenyl.
  • D very particularly preferably represents 2-pyrrolyl or 3-pyrrolyl which is optionally mono- or disubstituted, identically or differently, by fluorine, chlorine, CH 3 or C 2 H 5 , or for phenyl substituted by CHO, cyano, carboxyl, di-C 1 -C 6 alkoxy-C 1 -C 4 alkyl or C 1 -C 8 alkoxycarbonyl.
  • A is particularly emphasized for single or double, identical or different phenyl substituted by fluorine or chlorine.
  • D is particularly emphasized for 2- or 3-pyrrolyl which is optionally substituted once or twice, identically or differently, by fluorine, chlorine, methyl or ethyl, or for CHO, cyano, carboxyl, di-C 1 -C 6 -alkoxy-C 1 -C 4 alkyl or C 1 -C 6 alkoxycarbonyl substituted phenyl.
  • the active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which protect in agriculture, in forests, in the supply and material and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Thysanura e.g. Lepisma saccharina.
  • Isoptera for example Reticulitermes spp ..
  • Anoplura for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp ..
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodoniphasis, spp.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodoniphasis,
  • Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
  • Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.
  • Antho nomus spp. Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,
  • Niptus hololeucus Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon solsti tialis,
  • Costelytra zealandica From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • the active compounds according to the invention are notable for high insecticidal and acaricidal activity.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents Agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is to say liquid solvents and / or solid carriers
  • surface-active agents Agents ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; suitable dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue, and organic dyes, such as alizarin, azo and metal phthalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamid, tricyclazole, tridemorph, triflorolizol, triflorolizol, triflorolizole,
  • Bacillus thuringiensis Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Fufionproxophon, Flufenproxionfon, Flufenproxionfon, Flufenproxionfon, Flufenproxionfon, Flufenproxionfon, Flufenproxionfon, Fufenproxionfon, Fufionproxophon, Fufionproxophon, Fufionproxophon, Fufionprox, Fufionprox, Fufionprox, Fufionprox, Fungionfoxx
  • Imidacloprid Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin, Lamda-cyhalothrin, Lufenuron,
  • Methami dophos methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
  • Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M Primiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quiproxifen
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium
  • Aryl carboxylic acids e.g. Dichlorpicoic acid, dicamba and picloram
  • Aryloxyalkanoic acids e.g. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr
  • Aryloxy-phenoxyalkanoic acid esters e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl,
  • Haloxyfop-methyl and quizalofop-ethyl e.g. Chloridazon and norflurazon; Carbamates, e.g. Chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides, e.g. Alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines, e.g. Oryzalin, pendimethalin and trifluralin; Diphenyl ethers, e.g.
  • Oxyacetamides e.g. Mefenacet
  • Sulfonylureas e.g. Amidosulfuron, ben
  • Triazines e.g. Atrazin, cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, such as Aminotriazole, Benfuresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
  • the active ingredient according to the invention can also be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredient When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
  • reaction mixture After cooling, the reaction mixture is mixed with 45 ml of titanium IV chloride (1 molar solution in dichloromethane) and saturated with dry hydrogen chloride gas in an autoclave at room temperature. Then ethylene is introduced at about 0 ° C. for about 20 to 30 minutes and then stirred for 24 hours at 70 ° C. and about 14 bar internal pressure. The reaction mixture is stirred with about 150 ml of ice water, made alkaline at 0 ° C. with sodium hydroxide solution and extracted several times with dichloromethane. The combined organic phases are dried over magnesium sulfate and concentrated.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cabbage cockroach (Plutella maculipennis) while the leaves are still moist.
  • the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • Example IIa-5 the compound according to Example IIa-5, with an exemplary active compound concentration of 0J%, caused 100% killing after 7 days.

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  • Plant Pathology (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

A new process has been discovered for the production of partly known 5,6-dihydro-1,3-oxazines of the formula (I) in which A is substituted phenyl or possibly substituted naphthyl, pyridyl, thienyl or pyrazolyl and B is hydrogen, alkyl, alkoxy alkyl, alkyl thioalkyl, halogen alkyl, alkenyl, possibly substituted cycloalkyl of possibly substituted phenyl, phenyl alkyl, phenyl alkenyl, phenoxy alkyl, phenyl thioalkyl, pyridyl, 2- or 3-pyrrolyl, by reacting amide derivatives of the formula (II) with ethylene in the presence of gaseous hydrogen chloride and a catalyst. The novel 5,6-dihydro-1,3-oxazines are suitable for combatting animal pests.

Description

Verfahren zur Herstellung von 5,6-Dihydro-1,3-oxazinen  Process for the preparation of 5,6-dihydro-1,3-oxazines
Die Erfindung betrifft ein neues Verfahren zur Herstellung von teilweise bekannten 5,6-Dihydro-1,3-oxazinen, neue 5,6-Dihydro-1,3-oxazine, sowie neue Zwischenprodukte zu ihrer Herstellung und ihre Verwendung zur Bekämpfung tierischer Schädlinge. The invention relates to a new process for the preparation of partially known 5,6-dihydro-1,3-oxazines, new 5,6-dihydro-1,3-oxazines, as well as new intermediates for their preparation and their use for controlling animal pests.
Es ist bekannt, daß man 5,6-Dihydro-1,3-oxazine erhält, wenn man Aminoalkohole der Formel (A) mit Carbonsäuren der Formel (B) in Gegenwart eines wasserentziehenden Mittels gemäß dem folgenden Reaktionsschema umsetzt: It is known that 5,6-dihydro-1,3-oxazines are obtained if amino alcohols of the formula (A) are reacted with carboxylic acids of the formula (B) in the presence of a dehydrating agent in accordance with the following reaction scheme:
Figure imgf000003_0001
Figure imgf000003_0001
(vgl. hierzu EP-A 0 635 500 und WO-A 94/14783)  (cf. EP-A 0 635 500 and WO-A 94/14783)
Weiter ist bekannt, daß man 5,6-Dihydro-1,3-oxazine erhält, wenn man Aminoalkohole der Formel (A) zunächst mit Säurechloriden der Formel (C) umsetzt und anschließend die entstehenden Amidalkohole der Formel (D) mit einem wasserentziehenden Mittel gemäß dem folgenden Reaktionsschema cyclisiert: It is also known that 5,6-dihydro-1,3-oxazines are obtained if amino alcohols of the formula (A) are first reacted with acid chlorides of the formula (C) and then the resulting amide alcohols of the formula (D) with a dehydrating agent Cyclized according to the following reaction scheme:
Figure imgf000003_0002
Figure imgf000003_0002
(vgl. hierzu EP-A 0 635 500 und WO-A 94/14783) (cf. EP-A 0 635 500 and WO-A 94/14783)
Ferner ist bekannt, daß man 5,6-Dihydro-1,3-oxazine erhält, wenn man Aminoalkohole der Formel (E) mit Nitrilen der Formel (F) in Gegenwart von Rhodium- Komplexen, gegebenenfalls unter Zusatz von Diphosphinen gemäß dem folgenden Reaktionsschema umsetzt: It is also known that 5,6-dihydro-1,3-oxazines are obtained if amino alcohols of the formula (E) with nitriles of the formula (F) in the presence of rhodium Complexes, optionally with the addition of diphosphines according to the following reaction scheme:
Figure imgf000004_0001
Bei diesen bekannten Synthesemethoden sind jedoch - vor allem mit Blick auf das
Figure imgf000004_0001
In these known synthetic methods, however - especially with a view to
Gesamtverfahren, d.h. unter Einschluß der Herstellung der als Ausgangsstoffe benötigten Aminoalkohole der Formeln (A) bzw. (E) - die erzielbaren Ausbeuten der Produkte nicht zufriedenstellend: Die Aminoalkohole sind nur über mehrere Stufen, unter Verwendung teurer Vorprodukte und Reduktionsmittel in unbefriedi- genden Ausbeuten erhältlich, wobei aufgrund größerer Mengen an Reduktionsund Lösungsmitteln und dem teil weisen Arbeiten unter Inertgas zusätzliche technische Schwierigkeiten auftreten. Overall process, i.e. including the production of the amino alcohols of the formulas (A) or (E) required as starting materials - the yields of the products which can be achieved are unsatisfactory: the amino alcohols can only be obtained in unsatisfactory yields over several stages, using expensive precursors and reducing agents, where Due to larger amounts of reducing agents and solvents and the partial work under inert gas, additional technical difficulties arise.
Es wurde nun gefunden, daß man 5,6-Dihydro-1,3-oxazine der Formel (I) It has now been found that 5,6-dihydro-1,3-oxazines of the formula (I)
Figure imgf000004_0002
Figure imgf000004_0002
in welcher  in which
A für substituiertes Phenyl oder für jeweils gegebenenfalls substituiertes Naphthyl, Pyridyl, Thienyl oder Pyrazolyl steht und A stands for substituted phenyl or for optionally substituted naphthyl, pyridyl, thienyl or pyrazolyl and
B für Wasserstoff, Alkyl, Alkoxyalkyl, Alkylthioalkyl, Halogenalkyl, Alkenyl, gegebenenfalls substituiertes Cycloalkyl oder jeweils gegebenenfalls substi- tuiertes Phenyl, Phenylalkyl, Phenylalkenyl, Phenoxyalkyl, Phenylthioalkyl,B for hydrogen, alkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, optionally substituted cycloalkyl or in each case optionally substituted phenyl, phenylalkyl, phenylalkenyl, phenoxyalkyl, phenylthioalkyl,
Pyridyl, 2- oder 3-Pyrrolyl steht, erhält, wenn man Amid-Derivate der Formel (II) Pyridyl, 2- or 3-pyrrolyl, obtained if amide derivatives of the formula (II)
Figure imgf000005_0001
Figure imgf000005_0001
in welcher A und B die oben angegebene Bedeutung haben und in which A and B have the meaning given above and
R1 und R2 gleich oder verschieden sind und jeweils für Alkyl stehen oder R 1 and R 2 are the same or different and each represents alkyl or
gemeinsam mit dem N-Atom, an das sie gebunden sind, für einen gegebenenfalls substituierten Heterocyclus stehen, mit Ethylen in Gegenwart von Chlorwasserstoff-Gas und eines Katalysators, ge- gebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.  together with the N atom to which they are attached represent an optionally substituted heterocycle, with ethylene in the presence of hydrogen chloride gas and a catalyst, optionally in the presence of a diluent.
Überraschenderweise können nach dem erfindungsgemäßen Verfahren 5,6-Dihy- dro-1,3-oxazine der Formel (I) in guten Ausbeuten und in hoher Reinheit erhalten werden, obwohl aufgrund der geringen Reaktivität des Ethylens keine merkliche Reaktion zu erwarten war. Die erfindungsgemäße Umsetzung hat somit den Vorteil einer günstigeren Verfahrensdurchführung bei gleichzeitiger Ausbeuteverbesserung, insbesondere im Hinblick auf das Gesamtverfahren, d.h. unter Einbeziehung der Voφroduktherstellung (vgl. auch die Herstellungsbeispiele). Surprisingly, 5,6-dihydro-1,3-oxazines of the formula (I) can be obtained in good yields and in high purity by the process according to the invention, although no noticeable reaction was to be expected due to the low reactivity of the ethylene. The implementation according to the invention thus has the advantage of a more cost-effective process implementation with simultaneous improvement in yield, in particular with regard to the overall process, i.e. including the manufacture of the product (see also the manufacturing examples).
Die erfindungsgemäß herzustellenden Verbindungen sind durch die Formel (I) allgemein definiert. Bevorzugte Substituenten bzw. Bereiche der in den oben und nachstehend erwähnten Formeln aufgeführten Reste werden im folgenden erläutert. The compounds to be prepared according to the invention are generally defined by the formula (I). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.
A steht bevorzugt für Phenyl, das einfach bis fünffach, gleich oder verschieden substituiert ist durch Halogen, C1-C6-Alkyl, C1-C6-Alkoxy, C1-C6- Alkylthio, C1-C6-Halogenalkyl, C1-C6-Halogenalkoxy, C1-C6-Halogenalkyl- thio, Nitro, Cyano oder durch gegebenenfalls einfach bis fünffach, gleich oder verschieden durch Halogen, C1-C6-Alkyl, C1-C6-Halogenalkyl, C1-C6- Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkylthio oder C1-C6-Halogenalkyl- thio substituiertes Phenyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Halogen, C1-C6-Alkyl, C1-C6-Alkoxy oder C1-C6-Halogenalkoxy substituiertes Naphthyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Halogen, C1-C6- Alkyl, C1-C6-Alkoxy, C1-C6-Halogenalkyl, C1-C6-Halogen- alkoxy oder Cyano substituiertes Pyridyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Halogen oder C1-C6- Alkyl substituiertes Thienyl, oder für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Halogen oder C1-C3-Alkyl substituiertes Pyrazolyl. steht bevorzugt für Wasserstoff, C1-C6- Alkyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkylthio-C1-C6-alkyl, C1-C6-Halogenalkyl oder C2-C6-Alkenyl, für gegebenenfalls einfach bis fünffach, gleich oder verschieden durch Halogen, C1-C6-Alkyl, C1-C6-Alkoxy, C1-C6-Halogenalkyl oder C1-C6-Halo- genalkoxy substituiertes C3-C7-Cycloalkyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Halogen, C1-C6-Alkyl, C1-C6-Alkoxy, C1-C6-Halogenalkyl, C1-C6-Halogenalkoxy oder Cyano substituiertes Pyridyl, für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Halogen oder C 1-C4-Alkyl substituiertes α-Pyrrolyl oder ß-Pyrrolyl, für durch Hydroxy, CHO, Cyano, Carboxyl, Poly-C1-C8-alkoxy-C1-C8-alkyl oder C1-C8-Alkoxycarbonyl substituiertes Phenyl oder für jeweils gegebenenfalls einfach bis fünffach, gleich oder verschieden imA preferably represents phenyl which is monosubstituted to pentasubstituted by identical or different halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 - alkylthio, C 1 -C 6 haloalkyl , C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkylthio, nitro, cyano or by optionally single to fivefold, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl , C 1 -C 6 - Alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio substituted phenyl, for optionally mono- to triple, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy substituted naphthyl, for optionally single to triple, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 -Halogenalkyl, C 1 -C 6 -haloalkoxy or cyano substituted pyridyl, for optionally monosubstituted to trisubstituted, identically or differently, by halogen or C 1 -C 6 -alkyl-substituted thienyl, or for optionally monosubstituted to triple, identically or differently pyrazolyl substituted by halogen or C 1 -C 3 alkyl. preferably represents hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, C 1 -C 6 -Halogenalkyl or C 2 -C 6 -alkenyl, for optionally single to fivefold, identical or different by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkyl or C 1 - C 6 -C haloalkoxy substituted C 3 -C 7 cycloalkyl, for optionally single to triple, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl , C 1 -C 6 haloalkoxy or cyano substituted pyridyl, for each optionally mono- or disubstituted, identically or differently, by halogen or C 1 -C 4 alkyl substituted α-pyrrolyl or ß-pyrrolyl, for by hydroxy, CHO, cyano, Carboxyl, poly-C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl or C 1 -C 8 -alkoxycarbonyl-substituted phenyl or for each optionally optionally up to five times, identical or different in
Phenylring substituiertes Phenyl, Benzyl, Pheneth-1-yl, Pheneth-2-yl, Phen oxymethyl, Phenylthiomethyl, Phenylthioeth-1-yl, Phenoxyeth-1-yl, Phen- oxyeth-2-yl oder Styryl, wobei jeweils als Substituenten in Frage kommenPhenyl ring substituted phenyl, benzyl, pheneth-1-yl, pheneth-2-yl, phen oxymethyl, phenylthiomethyl, phenylthioeth-1-yl, phenoxyeth-1-yl, phenoxyeth-2-yl or styryl, where in each case are suitable as substituents
Halogen, Halogen,
C1-C18-Alkyl, C 1 -C 18 alkyl,
C1-C8-Alkoxy-C1-C8-alkyl, C 1 -C 8 alkoxy-C 1 -C 8 alkyl,
C1-C8-Halogenalkoxy, C 1 -C 8 haloalkoxy,
C1-C4-Halogenalkyl, C 1 -C 4 haloalkyl,
C1-C18-Alkoxy, das gegebenenfalls durch weitere 1 bis 3 Sauerstoffatome unterbrochen ist, C 1 -C 18 alkoxy, which is optionally interrupted by a further 1 to 3 oxygen atoms,
C1-C18-Alkylthio, C 1 -C 18 alkylthio,
C1-C8-Halogenalkylthio, C 1 -C 8 haloalkylthio,
Tri-(C1-C8)-alkylsilyl, Tri- (C 1 -C 8 ) alkylsilyl,
Phenyl-di-(C1-C8)-alkylsilyl, Phenyl-di- (C 1 -C 8 ) alkylsilyl,
3,4-Difluormethylendioxo,  3,4-difluoromethylene dioxo,
3 ,4-Tetrafluorethylendioxo, 3, 4-tetrafluoroethylene dioxo,
eine anellierte Benzogruppe,  a fused benzo group,
eine anellierte C3-C4-Alkandiylgruppe, gegebenenfalls durch Halogen, C1-C4-Alkyl oder C3-C6-Cycloalkyl substituiertes Benzyliminooxymethyl, jeweils gegebenenfalls durch C1-C6-Alkyl, C1-C6-Alkoxy, Cyclohexyl odera fused C 3 -C 4 alkanediyl group, optionally substituted by halogen, C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, benzyliminooxymethyl, in each case optionally by C 1 -C 6 alkyl, C 1 -C 6 alkoxy , Cyclohexyl or
Phenyl substituiertes Cyclohexyl oder Cyclohexyloxy, gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Halogen, C1-C4-Alkyl oder C1-C4-Halogenalkyl substituiertes Pyridyloxy, jeweils gegebenenfalls einfach bis fünffach, gleich oder verschieden durch Halogen, C1-C12-Alkyl, C1-C4-Halogenalkyl, C1-C12-Alkoxy, C1-C6-Halo- genalkoxy, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkoxy-ethylenoxy, C1-C6- Alkylthio oder C1-C6-Halogenalkylthio substituiertes Phenyl, Phenyl-C1-C6- alkyl, Phenoxy, Phenylthio, Phenyl-C1-C6-alkyloxy oder Benzylthio. steht besonders bevorzugt für Phenyl, das einfach bis vierfach, gleich oder verschieden substituiert ist durch Fluor, Chlor, Brom, C1-C3-Alkyl, C1-C3-Phenyl-substituted cyclohexyl or cyclohexyloxy, optionally mono- or disubstituted, identically or differently by halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl-substituted pyridyloxy, in each case optionally mono- to quintuple, identically or differently by halogen, C 1 - C 12 alkyl, C 1 -C 4 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 - C 6 alkoxy ethyleneoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio substituted phenyl, phenyl C 1 -C 6 alkyl, phenoxy, phenylthio, phenyl C 1 -C 6 alkyloxy or benzylthio . particularly preferably represents phenyl which is monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, bromine, C 1 -C 3 -alkyl, C 1 -C 3 -
Alkoxy, C1-C3-Alkylthio, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2-Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4-Alk- oxy, SCF3, SCHF2, Nitro, Cyano, oder durch gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, einfach bis fünffach, gleich oder verschie- den durch Fluor oder Chlor substituiertes C1-C2- Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4- Alkoxy, SCF3 oder SCHF2 substituiertes Phenyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Fluor, Chlor, C1-C6-Alkyl, C1-C6-Alkoxy oder einfach bis dreifach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C6-Alkoxy substituiertes Naphthyl, für gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor, C1-C3-Alkyl, C1-C3-Alkoxy, CF3, OCF3 oder Cyano substituiertes Pyridyl, für gegebenenfalls einfach oder zweifach, gleich oder verschieden durchAlkoxy, C 1 -C 3 alkylthio, single to five times, identical or different C 1 -C 2 alkyl substituted by fluorine or chlorine, single to five times, identical or different substituted by fluorine or chlorine C 1 -C 4 alkoxy, SCF 3 , SCHF 2 , nitro, cyano, or by optionally up to four times, identical or different by fluorine, chlorine, bromine, C 1 -C 4 -Alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, simple to five times, identical or different C 1 -C 2 -alkyl substituted by fluorine or chlorine, simple to five times, identical or different by fluorine or chlorine substituted C 1 -C 4 alkoxy, SCF 3 or SCHF 2 substituted phenyl, for optionally single to triple, identical or different by fluorine, chlorine, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or simple to triple, identical or different, substituted by fluorine or chlorine-substituted C 1 -C 6 alkoxy naphthyl, for optionally single or double, identical or different by fluorine, chlorine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy , CF 3 , OCF 3 or cyano substituted pyridyl, for optionally single or double, identical or different eden through
Chlor, Brom, Methyl oder Ethyl substituiertes Thienyl oder für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Fluor, Chlor, Brom oder C1-C3-Alkyl substituiertes Pyrazolyl. steht besonders bevorzugt für Wasserstoff C1-C4-Alkyl, C1-C4-Alkoxy-C1- C4-alkyl, C1-C4-Alkylthio-C1-C4-alkyl, C1-C4-Halogenalkyl oder C2-C6-Chlorine, bromine, methyl or ethyl-substituted thienyl or pyrazolyl which is optionally monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine or C 1 -C 3 -alkyl. particularly preferably represents hydrogen C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 - C 4 alkyl, C 1 -C 4 alkylthio-C 1 -C 4 alkyl, C 1 -C 4 Haloalkyl or C 2 -C 6 -
Alkenyl, für jeweils gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C3-Alkyl, C1-C3-Alkoxy, CF3 oder OCF3 substituiertes Cyclopropyl, Cyclopentyl oder Cyclohexyl, für gegebenenfalls einfach oder zweifach, gleich oder verschieden durchAlkenyl, for each optionally single to triple, identical or different, fluorine, chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, CF 3 or OCF 3 substituted cyclopropyl, cyclopentyl or cyclohexyl, for optionally single or twice, the same or different
Fluor, Chlor, C1-C3-Alkyl, C1-C3-Alkoxy, CF3, OCF3 oder Cyano substituiertes Pyridyl, für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor oder C1-C3-Alkyl substituiertes α-Pyrrolyl oder ß- Pyrrolyl, für durch CHO, Cyano, Hydroxy, Carboxyl, Poly-C1-C8-alkoxy-C1-C6-alkyl oder C1-C8-Alkoxycarbonyl substituiertes Phenyl oder für jeweils gegebenenfalls einfach bis vierfach, gleich oder verschieden im Phenylring substituiertes Phenyl, Benzyl, Pheneth-1-yl, Pheneth-2-yl, Phen- oxymethyl, Phenylthiomethyl, Phenylthioeth-1-yl, Phenoxyeth-1-yl, Phen- oxyeth-2-yl, oder Styryl, wobei jeweils als Substituenten in Frage kommen Fluor, Chlor, Brom, Fluorine, chlorine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, CF 3 , OCF 3 or cyano substituted pyridyl, for each optionally mono- or disubstituted, identically or differently, by fluorine, chlorine or C 1 -C 3 alkyl-substituted α-pyrrolyl or ß-pyrrolyl, by CHO, cyano, hydroxy, carboxyl, poly-C 1 -C 8 alkoxy -C 1 -C 6 -alkyl or C 1 -C 8 -alkoxycarbonyl-substituted phenyl or phenyl, benzyl, pheneth-1-yl, pheneth-2-yl, phen- oxymethyl, phenylthiomethyl, phenylthioeth-1-yl, phenoxyeth-1-yl, phenoxyeth-2-yl, or styryl, where in each case fluorine, chlorine, bromine are suitable as substituents,
C1-C18-Alkyl, C 1 -C 18 alkyl,
C1-C6-Alkoxy-C1-C8-alkyl, C 1 -C 6 alkoxy-C 1 -C 8 alkyl,
einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C8-Alkoxy, single to six-fold, identical or different C 1 -C 8 alkoxy substituted by fluorine or chlorine,
einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2-Alkyl, C 1 -C 2 alkyl mono- to quintuple, identical or different, substituted by fluorine or chlorine,
C1-C18-Alkoxy oder -(OC2H4)1-3-O-C1-C6-alkyl, C 1 -C 18 alkoxy or - (OC 2 H 4 ) 1-3 -OC 1 -C 6 alkyl,
C1-C15-Alkylthio, C 1 -C 15 alkylthio,
einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C8-Alkylthio, single to six-fold, identical or different C 1 -C 8 -alkylthio substituted by fluorine or chlorine,
Tri-(C1-C6)-alkylsilyl, Tri- (C 1 -C 6 ) alkylsilyl,
Phenyl-di-(C1-C6)-alkylsilyl, Phenyl-di- (C 1 -C 6 ) alkylsilyl,
3,4-Difluormethylendioxo,  3,4-difluoromethylene dioxo,
3,4-Tetrafluorethylendioxo,  3,4-tetrafluoroethylene dioxo,
eine anellierte Benzogruppe,  a fused benzo group,
eine anellierte C4-Alkandiylgruppe, a fused C 4 alkanediyl group,
die Gruppen the groups
Figure imgf000010_0001
Figure imgf000010_0001
jeweils gegebenenfalls durch C1-C4-Alkyl, C1-C4-Alkoxy, Cyclohexyl oder Phenyl substituiertes Cyclohexyl oder Cyclohexyloxy, each cyclohexyl or cyclohexyloxy optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclohexyl or phenyl,
gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor oder CF3 substituiertes Pyridyloxy, optionally pyridyloxy substituted once or twice, identically or differently by fluorine, chlorine or CF 3 ,
jeweils gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C12-Alkyl, einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4-Alkyl, C1-C12- Alkoxy, einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4-Alkoxy, C1-C4-Alkoxy-C1-C4-alkyl, C1-C4-Alkoxyethylenoxy, C1-C4-Alkylthio oder einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4-Alkylthio substituiertes Phenyl, Phenyl -C1-C6-alkyl, Phenoxy, Phenylthio, Phenyl-C1-C6- alkyloxy oder Benzylthio. A steht ganz besonders bevorzugt für Phenyl, das einfach bis dreifach, gleich oder verschieden substituiert ist durch Fluor, Chlor, Brom, C1-C3-Alkyl, C1-C3-Alkoxy, C1-C3-Alkylthio, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2-Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4- Alkoxy, SCF3, SCHF2, Nitro, Cyano, oder durch gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C3-Alkyl, C1-C3-Alkoxy, C1-C3-Alkylthio, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2-Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1- C4-Alkoxy, SCF3 oder SCHF2 substituiertes Phenyl. each optionally optionally up to four times, identical or different, by fluorine, chlorine, bromine, C 1 -C 12 -alkyl, single to six times, identical or different, substituted by fluorine or chlorine, C 1 -C 4 -alkyl, C 1 -C 12 - Alkoxy, simple to sixfold, identical or different, substituted by fluorine or chlorine, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkoxyethyleneoxy, C 1 -C 4- alkylthio or monosubstituted to sixfold, identically or differently, C 1 -C 4 -alkylthio substituted by fluorine or chlorine, phenyl, phenyl-C 1 -C 6 -alkyl, phenoxy, phenylthio, phenyl-C 1 -C 6 -alkyloxy or Benzylthio. A very particularly preferably represents phenyl which is monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, simple up to five times, identical or different C 1 -C 2 -alkyl substituted by fluorine or chlorine, single to five times, identical or different C 1 -C 4 -alkoxy substituted by fluorine or chlorine - alkoxy, SCF 3 , SCHF 2 , nitro, cyano, or by optionally one to four times, identical or different by fluorine, chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, simple to five times, identical or different by fluorine or chlorine-substituted C 1 -C 2 -alkyl which is monosubstituted to pentasubstituted by identical or different fluorine or chlorine-substituted C 1-2 substituted phenyl C 4 alkoxy, SCF 3 or SCHF.
B steht ganz besonders bevorzugt für Wasserstoff, C1-C4-Alkyl, C1-C2-B very particularly preferably represents hydrogen, C 1 -C 4 alkyl, C 1 -C 2 -
Alkoxy-C1-C4-alkyl, C1-C2-Alkylthio-C1-C4-alkyl, C1-C2-Halogenalkyl oder C2-C4-Alkenyl, für jeweils gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Fluor, Chlor, CH3, C2H5, OCH3, CF3 oder OCF3 substituiertes Cyc- lopropyl, Cyclopentyl oder Cyclohexyl, für gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor, CH3, C2H5, OCH3, CF3, OCF3 oder Cyano substituiertesAlkoxy-C 1 -C 4 alkyl, C 1 -C 2 alkylthio-C 1 -C 4 alkyl, C 1 -C 2 haloalkyl or C 2 -C 4 alkenyl, for cyclopropyl, cyclopentyl or cyclohexyl which are optionally monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, CH 3 , C 2 H 5 , OCH 3 , CF 3 or OCF 3 , for optionally mono- or disubstituted, identically or differently by Fluorine, chlorine, CH 3 , C 2 H 5 , OCH 3 , CF 3 , OCF 3 or cyano substituted
Pyridyl, für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor, CH3 oder C2H5 substituiertes α-Pyrrolyl oder ß- Pyrrolyl, für durch CHO, Hydroxy, Cyano, Carboxyl, Di-C1-C6-alkoxy-C1-C4-alkyl oder C1-C8-Alkoxycarbonyl substituiertes Phenyl oder für jeweils gegebenenfalls einfach bis dreifach, gleich oder verschieden im Phenylring substituiertes Phenyl, Benzyl, Pheneth-1-yl, Pheneth-2-yl, Phen- oxymethyl, Phenylthiomethyl, Phenylthioeth-1-yl, Phenoxyeth-1-yl, Phen- oxyeth-2-yl, oder Styryl, wobei jeweils als Substituenten in Frage kommenPyridyl, for each optionally mono- or disubstituted, identically or differently, by fluorine, chlorine, CH 3 or C 2 H 5, α-pyrrolyl or β-pyrrolyl, by CHO, hydroxy, cyano, carboxyl, di-C 1 -C 6 alkoxy-C 1 -C 4 -alkyl or C 1 -C 8 -alkoxycarbonyl-substituted phenyl or for phenyl, benzyl, pheneth-1-yl, pheneth-2-yl which are optionally monosubstituted to trisubstituted identically or differently in the phenyl ring, Phenoxymethyl, phenylthiomethyl, phenylthioeth-1-yl, phenoxyeth-1-yl, phenoxyeth-2-yl, or styryl, where in each case are suitable as substituents
Fluor, Chlor, Brom, Fluorine, chlorine, bromine,
C1-C18-Alkyl, C 1 -C 18 alkyl,
C1-C6-Alkoxy-C1-C8-alkyl, C 1 -C 6 alkoxy-C 1 -C 8 alkyl,
einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor sub- stituiertes C1-C8-Alkoxy, single to six-fold, identical or different C 1 -C 8 -alkoxy substituted by fluorine or chlorine,
einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2-Alkyl, C 1 -C 2 alkyl mono- to quintuple, identical or different, substituted by fluorine or chlorine,
C1-C18-Alkoxy oder -(OC2H4) 1-3-O-C1-C6-alkyl, C 1 -C 18 alkoxy or - (OC 2 H 4 ) 1-3 -OC 1 -C 6 alkyl,
C1-C15-Alkylthio, C 1 -C 15 alkylthio,
einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C8-Alkylthio, single to six-fold, identical or different C 1 -C 8 -alkylthio substituted by fluorine or chlorine,
Tri-(C1-C6)-alkylsilyl, Tri- (C 1 -C 6 ) alkylsilyl,
Phenyl-di-(C1-C6)-alkylsilyl, Phenyl-di- (C 1 -C 6 ) alkylsilyl,
3,4-Difluormethylendioxo,  3,4-difluoromethylene dioxo,
3,4-Tetrafluorethylendioxo,  3,4-tetrafluoroethylene dioxo,
eine anellierte Benzogruppe,  a fused benzo group,
eine anellierte C4-Alkandiylgruppe, a fused C 4 alkanediyl group,
die Gruppen
Figure imgf000012_0001
the groups
Figure imgf000012_0001
jeweils gegebenenfalls durch C1-C4-Alkyl, C1-C4-Alkoxy, Cyclohexyl oder Phenyl substituiertes Cyclohexyl oder Cyclohexyloxy, each cyclohexyl or cyclohexyloxy optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclohexyl or phenyl,
gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor oder CF3 substituiertes Pyridyloxy, optionally pyridyloxy substituted once or twice, identically or differently by fluorine, chlorine or CF 3 ,
jeweils gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C 12-Alkyl, einfach bis sechsfach durch Fluor oder Chlor substituiertes C1-C4-Alkyl, C1-C12- Alkoxy, einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4- Alkoxy, C1-C4-Alkoxy-C1-C4-alkyl, C1-C4-Alkoxy-ethylenoxy, C1-C4-Alkylthio oder einfach bis sechsfach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4-Alkylthio substituiertes Phenyl, Phenyl-C1-C6-alkyl, Phenoxy, Phenylthio, Phenyl-C1-C6 -alkyloxy oder Benzylthio. each optionally optionally up to four times, identical or different by fluorine, chlorine, bromine, C 1 -C 12 -alkyl, simply up to six times substituted by fluorine or chlorine, C 1 -C 4 -alkyl, C 1 -C 12 -alkoxy, simply to C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-ethyleneoxy, C 1 -C 4 - substituted six times, identically or differently, by fluorine or chlorine Alkylthio or simple to six-fold, identically or differently substituted by fluorine or chlorine, substituted C 1 -C 4 alkylthio substituted phenyl, phenyl-C 1 -C 6 alkyl, phenoxy, phenylthio, phenyl-C 1 -C 6 alkyloxy or benzylthio.
Bevorzugte, erfindungsgemäß herstellbare Verbindungen sind Stoffe der Formel (Ia) Preferred compounds which can be prepared according to the invention are substances of the formula (Ia)
Figure imgf000012_0002
Figure imgf000012_0002
in welcher in which
A für die oben genannten allgemeinen, vorzugsweisen, besonders bevorzugten und ganz besonders bevorzugten Bedeutungen steht und B1 für einfach bis fünffach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten die oben unter B für den Phenylrest als bevorzugt, besonders bevorzugt und ganz besonders bevorzugt genannten Substituenten in Frage kommen. A stands for the general, preferred, particularly preferred and very particularly preferred meanings mentioned above and B 1 represents mono- to pentasubstituted, identically or differently substituted phenyl, the substituents which may be mentioned as preferred, particularly preferred and very particularly preferred substituents under B for the phenyl radical.
Eine besonders bevorzugte Gruppe von erfindungsgemäß herstellbaren Stoffen sind Verbindungen der Formel (I) A particularly preferred group of substances which can be prepared according to the invention are compounds of the formula (I)
Figure imgf000013_0001
Figure imgf000013_0001
in welcher  in which
A für einfach oder zweifach, gleich oder verschieden durch Fluor oder Chlor substituiertes Phenyl steht und A represents phenyl substituted once or twice, identically or differently by fluorine or chlorine, and
B für einfach bis dreifach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C8- Alkyl, C1-C8-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, C1-C8-Alkylthio oder C3-C6-Cycloalkyl substituiertes Phenyl oder für einfach durch jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden im Phenylteil durch Fluor, Chlor, Brom, C1-C6-Alkyl, C1-C6-B for single to triple, identical or different by fluorine, chlorine, bromine, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 8 alkylthio or C 3 -C 6 cycloalkyl substituted phenyl or for monosubstituted by fluorine, chlorine, bromine, C 1 -C 6 alkyl, C 1 -C 6 in the phenyl part in each case optionally in single or double, identical or different -
Alkoxy, C1-C 4-Halogenalkyl oder C1-C4-Halogenalkoxy substituiertes Phenyl, Phenyl-C1-C3-alkyl, Phenyloxy oder Benzyloxy substituiertes Phenyl, für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor, Methyl, Ethyl oder Trifluormethyl substituiertes Pyridyl, 2- oder 3-Pyrrolyl oder für durch CHO, Hydroxy, Cyano, Carboxyl, Di-C1-C6-alkoxy-C1-C4-alkyl oder C1-C6-Alkoxycarbonyl substituiertes Phenyl steht. Alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy substituted phenyl, phenyl-C 1 -C 3 alkyl, phenyloxy or benzyloxy substituted phenyl, each optionally mono- or disubstituted, identically or differently, by fluorine, chlorine , Methyl, ethyl or trifluoromethyl substituted pyridyl, 2- or 3-pyrrolyl or for by CHO, hydroxy, cyano, carboxyl, di-C 1 -C 6 alkoxy-C 1 -C 4 alkyl or C 1 -C 6 - Alkoxycarbonyl substituted phenyl.
Verwendet man beispielsweise N-[Morpholin-4-yl-(4-tert.-butylphenyl)-methyl]- 2,6-difluorbenzamid und Ethylen als Ausgangsstoffe in Gegenwart von HCl-Gas und Titantetrachlorid als Katalysator, so kann der Reaktionsablauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema dargestellt werden: If, for example, N- [morpholin-4-yl- (4-tert-butylphenyl) methyl] - 2,6-difluorobenzamide and ethylene are used as starting materials in the presence of HCl gas and titanium tetrachloride as catalyst, the course of the reaction of the process according to the invention can be represented by the following formula:
Figure imgf000014_0001
Figure imgf000014_0001
Die beim erfindungsgemäßen Verfahren als Ausgangsstoffe zu verwendenden Amid-Derivate sind durch die Formel (II) allgemein definiert. In der Formel (II) haben A und B vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäß hertstellbaren Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für A und B angegeben wurden. R1 und R2 sind gleich oder verschieden und stehen vorzugsweise für C1-C4-Formula (II) provides a general definition of the amide derivatives to be used as starting materials in the process according to the invention. In formula (II), A and B preferably or in particular have those meanings which have already been given as preferred, particularly preferred or very particularly preferred for A and B in connection with the description of the compounds of the formula (I) which can be prepared according to the invention . R 1 and R 2 are the same or different and are preferably C 1 -C 4 -
Alkyl, insbesondere für Methyl, Ethyl, n- oder i-Propyl oder vorzugsweise gemeinsam mit dem N-Atom, an das sie gebunden sind, für einen gegebenenfalls einfach bis fünffach, bevorzugt einfach oder zweifach gleich oder verschieden substituierten 5- oder 6-gliedrigen Heterocyclus, der gegebenenfalls ein oder zwei weitereAlkyl, in particular for methyl, ethyl, n- or i-propyl or preferably together with the N atom to which they are attached, for a 5- or 6-membered group which is optionally monosubstituted to pentasubstituted, preferably monosubstituted or disubstituted, in the same or different manner Heterocycle, optionally one or two more
Heteroatome, bevorzugt ein weiteres Heteroatom, wie O, S oder NR enthalten kann, wobei als Substituenten insbesondere C1-C4-Alkyl und C1-C4-Alkoxy genannt seien und wobei R für Alkyl, vorzugsweise C1-C4- Alkyl, oder für gegebenenfalls substituiertes Aryl steht, insbesondere für gegebenenfalls einfach oder zweifach, gleich oder verschieden substituiertes Phenyl, wobei als Substituenten vorzugsweise genannt seien: Halogen, C1-C4- Alkyl, C1-C4-Halogenalkyl, C1-C4- Alkoxy, C1-C4-Halogenalkoxy, C1-C4-Alkylthio sowie C1-C4- Halogenalkylthio. Einige Amid-Derivate der Formel (II), in welchen B für Wasserstoff steht, sind bereits bekannt (vgl. z.B. Liebigs Annalen 343, 207 (1905) und Bull. Soc. Chim. France 1979, II, 409-414). Neu und ebenfalls Gegenstand dieser Anmeldung sind Amid-Derivate der Formel (Ila) Heteroatoms, preferably a further heteroatom, such as O, S or NR, may be mentioned as substituents, in particular C 1 -C 4 alkyl and C 1 -C 4 alkoxy and where R is alkyl, preferably C 1 -C 4 - Alkyl, or optionally substituted aryl, in particular optionally optionally mono- or disubstituted, identically or differently substituted phenyl, where the following may be mentioned as preferred substituents: halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 - C 4 - alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio and C 1 -C 4 - haloalkylthio. Some amide derivatives of the formula (II) in which B represents hydrogen are already known (cf., for example, Liebigs Annalen 343, 207 (1905) and Bull. Soc. Chim. France 1979, II, 409-414). New and also the subject of this application are amide derivatives of the formula (Ila)
Figure imgf000015_0001
Figure imgf000015_0001
in welcher A, R1 und R2 die oben angegebene Bedeutung haben und in which A, R 1 and R 2 have the meaning given above and
B2 die oben für B angegebene Bedeutung mit Ausnahme von Wasserstoff hat. B 2 has the meaning given for B with the exception of hydrogen.
Man erhält die Amid-Derivate der Formel (Ila) beispielsweise, indem man Amide der Formel (III) A-CO-NH2 (III) in welcher The amide derivatives of the formula (Ila) are obtained, for example, by amides of the formula (III) A-CO-NH 2 (III) in which
A die oben angegebene Bedeutung hat, mit Aldehyden der Formel (IV) A has the meaning given above, with aldehydes of the formula (IV)
B2-CHO (IV) B 2 -CHO (IV)
in welcher  in which
B2 die oben angegebene Bedeutung hat, und mit Aminen der Formel (V) B 2 has the meaning given above, and with amines of the formula (V)
Figure imgf000015_0002
Figure imgf000015_0002
in welcher R1 und R2 die oben angegebene Bedeutung haben, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt. in which R 1 and R 2 have the meaning given above, if appropriate in the presence of a diluent.
Verwendet man beispielsweise 2,6-Difluorbenzoesäureamid, 4-tert.-Butylbenzalde- hyd und Morpholin als Ausgangsstoffe, so kann der Reaktionsablauf des Verfahrens zur Herstellung der Amid-Derivate der Formel (II) durch das folgende Formelschema skizziert werden: If, for example, 2,6-difluorobenzoic acid amide, 4-tert-butylbenzaldehyde and morpholine are used as starting materials, the course of the reaction of the process for the preparation of the amide derivatives of the formula (II) can be outlined using the following formula:
Figure imgf000016_0001
Figure imgf000016_0001
Die zur Herstellung der Amid-Derivate der Formel (II) als Ausgangsstoffe benötigten Amide der Formel (III), Aldehyde der Formel (IV) und sekundären Amine der Formel (V) sind allgemein bekannt bzw. in allgemein bekannter Art und Weise erhältlich.  The amides of the formula (III), aldehydes of the formula (IV) and secondary amines of the formula (V) required as starting materials for the preparation of the amide derivatives of the formula (II) are generally known or can be obtained in a generally known manner.
Als Verdünnungsmittel kommen bei der Durchführung des Verfahrens zur Herstellung der Amid-Derivate der Formel (II) alle für derartige Umsetzungen üblichen, inerten orgenischen Solventien in Betracht. Vorzugsweise verwendbar sind Alkohole, wie Methanol oder Ethanol; Ester, wie Essigsäuremethylester oderSuitable diluents for carrying out the process for the preparation of the amide derivatives of the formula (II) are all inert organic solvents which are customary for such reactions. Alcohols such as methanol or ethanol can preferably be used; Esters, such as methyl acetate or
Essisäureethylester; Ether, wie Diethylether, Methyl-tert.-butyl-ether, Ethylen- glykol-dimethylether, Tetrahydrofuran oder Dioxan, ferner Nitrile, wie Acetonitril; außerdem gegebenenfalls halogenierte aliphatische, cycloaliphatische oder aromatische Kohlenwasserstoffe, wie Methylenchlorid, Chloroform, Tetrachlorkoh- lenstoff, Hexan, Cyclohexan, Benzol, Toluol, Xylol oder Chlorbenzol; sowieEthyl acetate; Ethers, such as diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, and also nitriles, such as acetonitrile; also optionally halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, hexane, cyclohexane, benzene, toluene, xylene or chlorobenzene; such as
Sulfoxide, wie Dimethylsulfoxid. Die Reaktionstemperaturen können bei der Durchführung des Verfahrens zur Herstellung der Amid-Derivate der Formel (II) innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0 und 120°C, vorzugsweise zwischen 10 und 100°C. Bei der Durchführung des Verfahrens zur Herstellung der Amid-Derivate derSulfoxides such as dimethyl sulfoxide. The reaction temperatures can be varied within a substantial range when carrying out the process for the preparation of the amide derivatives of the formula (II). In general, temperatures between 0 and 120 ° C, preferably between 10 and 100 ° C. When carrying out the process for the preparation of the amide derivatives
Formel (II) setzt man pro Mol Amid der Formel (III) im allgemeinen 1,0 bis 1,5 Mol, vorzugsweise 1,0 bis 1,2 Mol an Aldehyd der Formel (IV) sowie 1,0 bis 2,0 Mol, vorzugsweise 1,0 bis 1,2 Mol an sekundärem Amin der Formel (V) ein. Formula (II) is generally employed per mole of amide of formula (III) 1.0 to 1.5 moles, preferably 1.0 to 1.2 moles of aldehyde of formula (IV) and 1.0 to 2.0 moles , preferably 1.0 to 1.2 mol of secondary amine of the formula (V).
Die Reaktionsdurchführung, Aufarbeitung und Isolierung der Reaktionsprodukte erfolgt nach allgemein üblichen Methoden. The reaction is carried out, worked up and isolated according to generally customary methods.
Die Amid-Derivate der Formel (II) können gegebenenfalls auch direkt, d.h. ohne isoliert zu werden, gemäß dem erfindungsgemäßen Verfahren mit Ethylen zu den Endprodukten der Formel (I) umgesetzt werden (vgl. auch die Herstellungsbeispiele). Die neuen Amid-Derivate der Formel (Ila) zeigen auch gute biologische Wirkungen bei der Verwendung zur Bekämpfung von tierischen Schädlingen. The amide derivatives of formula (II) can optionally also be directly, i.e. without being isolated, are reacted with ethylene to give the end products of the formula (I) in the process according to the invention (cf. also the preparation examples). The new amide derivatives of the formula (Ila) also show good biological effects when used to control animal pests.
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der Formel (I) wird in Gegenwart von Chlorwasserstoff-Gas und eines Katalysators durchgeführt. Als Katalysatoren kommen Lewis-Säuren, vorzugsweise Übergangsmetallhaloge- nide in Frage, insbesondere Titantetrachlorid, Zinntetrachlorid und Zinkdichlorid. The process according to the invention for the preparation of the compounds of the formula (I) is carried out in the presence of hydrogen chloride gas and a catalyst. Lewis acids, preferably transition metal halides, in particular titanium tetrachloride, tin tetrachloride and zinc dichloride are suitable as catalysts.
Das erfindungsgemäße Verfahren wird vorzugsweise in Gegenwart eines Verdünnungsmittels durchgeführt. The process according to the invention is preferably carried out in the presence of a diluent.
Als Verdünnungsmittel kommen übliche organische Lösungsmittel in Betracht, z.B. gegebenenfalls halogenierte aliphatische, cycloaliphatische oder aromatische Kohlenwasserstoffe. Hierzu gehören beispielsweise Chlorbenzol, Dichlorbenzol,Suitable diluents are conventional organic solvents, e.g. optionally halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons. These include, for example, chlorobenzene, dichlorobenzene,
Petrolether, Hexan, Cyclohexan, Dichlormethan, Chloroform und Tetrachlormethan. Petroleum ether, hexane, cyclohexane, dichloromethane, chloroform and carbon tetrachloride.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -120°C und +120°C, vorzugsweise bei Temperaturen zwischen 10°C und 100°C. The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. Generally works one at temperatures between -120 ° C and + 120 ° C, preferably at temperatures between 10 ° C and 100 ° C.
Bei dieser Temperatur wird bevorzugt in einem geschlossenen Gefäß (Autoklaven) unter dem sich einstellenden Eigendruck der Reaktionsmischung gearbeitet. Es ist aber auch möglich, das Ethylen bei Normaldruck durch die Reaktionsmischung zu leiten, wobei man das nicht verbrauchte Ethylen gegebenenfalls im Kreislauf zurückführt. At this temperature it is preferred to work in a closed vessel (autoclave) under the autogenous pressure of the reaction mixture. However, it is also possible to pass the ethylene through the reaction mixture at atmospheric pressure, with the unused ethylene possibly being recycled.
Eine weitere Möglichkeit besteht darin, das Ethylen bei tiefen Temperaturen (ca. -1 10°C) einzukondensieren und die Reaktion bei dieser Temperatur durchzuführen. Zur Durchführung des erfindungsgemäßen Verfahrens setzt man pro Mol Amid-Another possibility is to condense the ethylene at low temperatures (approx. -1 10 ° C) and to carry out the reaction at this temperature. To carry out the process according to the invention, per mole of amide
Derivat der Formel (II) im allgmeinen zwischen 1 und 5 Mol, vorzugsweise zwischen 1 bis 3 Mol Ethylen und jeweils zwischen 1 und 5 Mol, vorzugsweise zwischen 1 bis 4 Mol Chlorwasserstoffgas sowie Katalysator ein. Derivative of formula (II) in general between 1 and 5 mol, preferably between 1 to 3 mol ethylene and in each case between 1 and 5 mol, preferably between 1 to 4 mol hydrogen chloride gas and catalyst.
Die Aufarbeitung kann auf übliche Weise durchgeführt werden; vorzugsweise wird das Reaktionsgemisch unter Kühlung bei Temperaturen zwischen 0°C und 10°C alkalisch gestellt und das Endprodukt in allgemein üblicher Art und Weise isoliert. The workup can be carried out in the usual way; the reaction mixture is preferably made alkaline with cooling at temperatures between 0 ° C. and 10 ° C. and the end product is isolated in a generally customary manner.
Die nach dem erfindungsgemäßen Verfahren herzustellenden 5,6-Dihydro-1,3- oxazine der Formel (I) sind weitgehend bekannt (vgl. z.B. EP-A 0 635 500 sowie WO-A 94/14783) und werden zur Bekämpfung von tierischen Schädlingen einge- setzt. The 5,6-dihydro-1,3-oxazines of the formula (I) to be prepared by the process according to the invention are largely known (cf., for example, EP-A 0 635 500 and WO-A 94/14783) and are used to control animal pests used.
Neu und ebenfalls Gegenstand der Erfindung sind Verbindungen der Formel (Ib) Compounds of the formula (Ib) are new and also an object of the invention.
Figure imgf000018_0001
Figure imgf000018_0001
in welcher  in which
A die oben angegebene Bedeutung hat und D für jeweils gegebenenfalls substituiertes 2- oder 3-Pyrrolyl oder für durchA has the meaning given above and D for each optionally substituted 2- or 3-pyrrolyl or for by
CHO, Cyano, Carboxyl, Polyalkoxyalkyl oder Alkoxycarbonyl substituiertes Phenyl steht. CHO, cyano, carboxyl, polyalkoxyalkyl or alkoxycarbonyl substituted phenyl.
Die Verbindungen der Formel (Ib) können - auch in Abhängigkeit von der Art der Substituenten - als geometrische und/oder optische Isomere oder Isomerengemische unterschiedlicher Zusammensetzung vorliegen. Die Erfindung betrifft sowohl die reinen Isomeren als auch die Isomerengemische. The compounds of the formula (Ib) can also be present as geometric and / or optical isomers or isomer mixtures of different compositions, depending on the nature of the substituents. The invention relates to both the pure isomers and the isomer mixtures.
Weiterhin wurde gefunden, daß sich die Verbindungen der Formel (Ib) nach dem oben beschriebenen erfindungsgemäßen Verfahren herstellen lassen. Schließlich wurde gefunden, daß die neuen Verbindungen der Formel (Ib) sehr gut zur Bekämpfung von tierischen Schädlingen, insbesondere von Arthropoden und Nematoden, geeignet sind. It has also been found that the compounds of the formula (Ib) can be prepared by the process according to the invention described above. Finally, it was found that the new compounds of the formula (Ib) are very suitable for controlling animal pests, in particular arthropods and nematodes.
Überraschenderweise zeigen die erfindungsgemäßen Verbindungen der Formel (Ib) eine erheblich bessere Wirksamkeit gegen tierische Schädlinge als die konstitutio- nell ähnlichsten bekannten Verbindungen. Surprisingly, the compounds of the formula (Ib) according to the invention show a considerably better activity against animal pests than the most similar known compounds in terms of constitution.
Die erfindungsgemäßen Verbindungen sind durch die Formel (Ib) allgemein definiert. The compounds of the invention are generally defined by the formula (Ib).
Bevorzugte Substituenten bzw. Bereiche der in den vorstehend und nachfolgend aufgeführten Formeln erwähnten Reste werden im folgenden erläutert. A steht bevorzugt für Phenyl, das einfach bis fünffach, gleich oder verschieden substituiert ist durch Halogen, C1-C6-Alkyl, C1-C6-Alkoxy, C1-C6- Alkylthio, C1-C6-Halogenalkyl, C1-C6-Halogenalkoxy, C1-C6-Halogenalkyl- thio, Nitro, Cyano oder durch gegebenenfalls einfach bis fünffach, gleich oder verschieden durch Halogen, C1-C8-Alkyl, C1-C8-Halogenalkyl, C1-C6- Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkylthio oder C1-C6-Halogenalkyl- thio substituiertes Phenyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes Naphthyl, wobei als Substituenten genannt seien Halogen, C1-C6-Alkyl, C1-C6-Alkoxy und C1-C6-Halogenalkoxy, für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes Pyridyl, wobei als Substituenten genannt seien Halogen, C1-C6-Alkyl, C1-C6-Alkoxy, C1-C6-Halogenalkyl, C1-C6-Halogenalkoxy und Cyano, für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituier- tes Thienyl, wobei als Substituenten genannt seien Halogen und C1-C6-Alkyl, oder für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes Pyrazolyl, wobei als Substituenten genannt seien Halogen oder C1-C3- Alkyl. D steht bevorzugt für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Halogen oder C1-C4-Alkyl substituiertes 2-Pyrrolyl oder 3-Pyrrolyl, oder für durch CHO, Cyano, Carboxyl, Poly-C1-C8-alkoxy-C1-C8-alkyl oder C1-C8-Alkoxycarbonyl substituiertes Phenyl. A steht besonders bevorzugt für Phenyl, das einfach bis vierfach, gleich oder verschieden substituiert ist durch Preferred substituents or ranges of the radicals mentioned in the formulas listed above and below are explained below. A preferably represents phenyl which is monosubstituted to pentasubstituted by identical or different halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 - alkylthio, C 1 -C 6 haloalkyl , C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkylthio, nitro, cyano or by optionally single to fivefold, identical or different by halogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl , C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio substituted phenyl, for optionally mono- to trisubstituted, identically or differently substituted, naphthyl, where halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 haloalkoxy may be mentioned as substituents, optionally monosubstituted to trisubstituted by identical or different substituted pyridyl, may be mentioned being the substituents halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy and cyano, for optionally monosubstituted to trisubstituted, identically or differently substituted thienyl, where substituents are halogen and C 1 -C 6 -alkyl, or for optionally monosubstituted to trisubstituted, identically or differently substituted, pyrazolyl, where substituents are mentioned Halogen or C 1 -C 3 alkyl. D preferably represents 2-pyrrolyl or 3-pyrrolyl, optionally substituted once or twice, identically or differently by halogen or C 1 -C 4 alkyl, or by CHO, cyano, carboxyl, poly-C 1 -C 8 alkoxy -C 1 -C 8 alkyl or C 1 -C 8 alkoxycarbonyl substituted phenyl. A particularly preferably represents phenyl which is monosubstituted to tetrasubstituted by identical or different substituents
Fluor, Chlor, Brom, C1-C3-Alkyl, C1-C3-Alkoxy, C1-C3-Alkylthio, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2-Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4-Alkoxy, SCF3, SCHF2, Nitro, Cyano, oder durch gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4- Alkylthio, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2 -Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C Alkoxy, SCF3 oder SCHF2 substituiertesFluorine, chlorine, bromine, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -alkylthio, simple to five-fold, identical or different C 1 -C 2 -alkyl substituted by fluorine or chlorine, C 1 -C 4 alkoxy, SCF 3 , SCHF 2 , nitro, cyano, substituted one to five times, identically or differently, by fluorine or chlorine, or by optionally up to four times, identically or differently, by fluorine, chlorine, bromine, C 1 - C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, simple to five times, identical or different C 1 -C 2 alkyl substituted by fluorine or chlorine, simple to five times, identical or different by fluorine or chlorine substituted C 1 -C alkoxy, SCF 3 or SCHF 2 substituted
Phenyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes Naphthyl, wobei als Substituenten genannt seien Phenyl, for naphthyl which may be monosubstituted to trisubstituted by identical or different substituents, where substituents are mentioned
Fluor, Chlor, C1-C6-Alkyl, C1-C6-Alkoxy und einfach bis dreifach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C6-Alkoxy, für gegebenenfalls einfach oder zweifach, gleich oder verschieden substituiertes Pyridyl, wobei als Substituenten genannt seien Fluorine, chlorine, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and mono- to triple, identical or different, C 1 -C 6 alkoxy substituted by fluorine or chlorine, for optionally mono- or disubstituted, identically or differently substituted pyridyl, where substituents are mentioned
Fluor, Chlor, C1-C3-Alkyl, C1-C3-Alkoxy, CF3, OCF3 und Cyano, für gegebenenfalls einfach oder zweifach, gleich oder verschieden substituiertes Thienyl, wobei als Substituenten genannt seien Fluorine, chlorine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, CF 3 , OCF 3 and cyano, for optionally mono- or disubstituted, identically or differently substituted thienyl, where substituents are mentioned
Chlor, Brom, Methyl, Ethyl oder für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes Pyrazolyl, wobei als Substituenten genannt seien  Chlorine, bromine, methyl, ethyl or pyrazolyl which is optionally monosubstituted to trisubstituted identically or differently, where substituents are mentioned
Fluor, Chlor, Brom und C1-C3-Alkyl. D steht besonders bevorzugt für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor oder C1-C3-Alkyl substituiertes 2-Pyrrolyl oder 3-Pyrrolyl, oder für durch CHO, Cyano, Carboxyl, Poly-C1-C8-alkoxy-C1-C6-alkyl oder C1-C8-Alkoxycarbonyl substituiertes Phenyl. A steht ganz besonders bevorzugt für Phenyl, das einfach bis dreifach, gleich oder verschieden substituiert ist durch Fluorine, chlorine, bromine and C 1 -C 3 alkyl. D particularly preferably represents 2-pyrrolyl or 3-pyrrolyl optionally substituted once or twice, identically or differently, by fluorine, chlorine or C 1 -C 3 -alkyl, or by CHO, cyano, carboxyl, poly-C 1 -C 8- alkoxy-C 1 -C 6 alkyl or C 1 -C 8 alkoxycarbonyl substituted phenyl. A very particularly preferably represents phenyl which is monosubstituted to trisubstituted by identical or different substituents
Fluor, Chlor, Brom, C1-C3-Alkyl, C1-C3-Alkoxy, C1-C3-Alkylthio, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2-Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4-Alkoxy, SCF3, SCHF2, Nitro, Cyano, oder durch gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, C1-C3-Alkyl, C1-C3-Alkoxy, C1-C3-Alkylthio, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C2- Alkyl, einfach bis fünffach, gleich oder verschieden durch Fluor oder Chlor substituiertes C1-C4- Alkoxy, SCF3 oder SCHF2 substituiertesFluorine, chlorine, bromine, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -alkylthio, simple to five-fold, identical or different C 1 -C 2 -alkyl substituted by fluorine or chlorine, C 1 -C 4 alkoxy, SCF 3 , SCHF 2 , nitro, cyano, substituted one to five times, identically or differently, by fluorine or chlorine, or by optionally up to four times, identically or differently, by fluorine, chlorine, bromine, C 1 - C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, simple to five times, identical or different C 1 -C 2 alkyl substituted by fluorine or chlorine, simple to five times, identical or different by fluorine or chlorine substituted C 1 -C 4 alkoxy, SCF 3 or SCHF 2 substituted
Phenyl. Phenyl.
D steht ganz besonders bevorzugt für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor, CH3 oder C2H5 substituiertes 2-Pyrrolyl oder 3-Pyrrolyl, oder für durch CHO, Cyano, Carboxyl, Di-C1-C6-alkoxy-C1-C4-alkyl oder C1-C8-Alkoxycarbonyl substituiertes Phenyl. D very particularly preferably represents 2-pyrrolyl or 3-pyrrolyl which is optionally mono- or disubstituted, identically or differently, by fluorine, chlorine, CH 3 or C 2 H 5 , or for phenyl substituted by CHO, cyano, carboxyl, di-C 1 -C 6 alkoxy-C 1 -C 4 alkyl or C 1 -C 8 alkoxycarbonyl.
A steht besonders hervorgehoben für einfach oder zweifach, gleich oder verschieden durch Fluor oder Chlor substituiertes Phenyl. D steht besonders hervorgehoben für jeweils gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Fluor, Chlor, Methyl oder Ethyl substituiertes 2- oder 3-Pyrrolyl, oder für durch CHO, Cyano, Carboxyl, Di-C1-C6-alkoxy-C1-C4-alkyl oder C1-C6-Alkoxycarbonyl substituiertes Phenyl. Die Wirkstoffe eignen sich zur Bekämpfung von tierischen Schädlingen, vorzugsweise Arthropoden und Nematoden, insbesondere Insekten und Spinnentieren, die in der Landwirtschaft, in Forsten, im Vorrats- und Material schütz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören: A is particularly emphasized for single or double, identical or different phenyl substituted by fluorine or chlorine. D is particularly emphasized for 2- or 3-pyrrolyl which is optionally substituted once or twice, identically or differently, by fluorine, chlorine, methyl or ethyl, or for CHO, cyano, carboxyl, di-C 1 -C 6 -alkoxy-C 1 -C 4 alkyl or C 1 -C 6 alkoxycarbonyl substituted phenyl. The active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which protect in agriculture, in forests, in the supply and material and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
Aus der Ordnung der Isopoda z.B. Oniscus asellus, Armadillidium vulgäre, Porcellio scaber. From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus. From the order of the Diplopoda e.g. Blaniulus guttulatus.
Aus der Ordnung der Chilopoda z.B. Geophilus carpophagus, Scutigera spec.  From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spec.
Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.  From the order of the Symphyla e.g. Scutigerella immaculata.
Aus der Ordnung der Thysanura z.B. Lepisma saccharina.  From the order of the Thysanura e.g. Lepisma saccharina.
Aus der Ordnung der Collembola z.B. Onychiurus armatus.  From the order of the Collembola e.g. Onychiurus armatus.
Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana,From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana,
Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria. Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
Aus der Ordnung der Dermaptera z.B. Forficula auricularia. From the order of the Dermaptera e.g. Forficula auricularia.
Aus der Ordnung der Isoptera z.B. Reticulitermes spp.. Aus der Ordnung der Anoplura z.B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.. From the order of the Isoptera, for example Reticulitermes spp .. From the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp ..
Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp. From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.
Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci. From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius,From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius,
Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Sais- setia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp. From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodoniphasis, spp. Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana. From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplocapsia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnidana, Homona magnidana.
Aus der Ordnung der Coleoptera z.B. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varive stis, Atomaria spp., Oryzaephilus surinamensis,From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephive, Orisamumisilamamililamamililamamililamamililamamililamamililamamililamaminilamamililamamililamasilpparum, Epilachnayamilamasilpparum
Antho nomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Antho nomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,
Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,
Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon solsti tialis,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon solsti tialis,
Costelytra zealandica. Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. Costelytra zealandica. From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp.,From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp.,
Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa. Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
Aus der Ordnung der Siphonaptera z.B. Xenopsylla cheopis, Ceratophyllus spp.. Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans. From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.
Aus der Ordnung der Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.. From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
Die erfindungsgemäßen Wirkstoffe zeichnen sich durch eine hohe insektizide und akarizide Wirksamkeit aus. The active compounds according to the invention are notable for high insecticidal and acaricidal activity.
Sie lassen sich mit besonders gutem Erfolg zur Bekämpfung von pflanzenschädigenden Insekten, wie beispielsweise gegen die Larven des Meerettich- blattkäfers (Phaedon cochleariae) oder gegen die Larven der grünen ReiszikadeThey can be used with particularly good success in combating plant-damaging insects, for example against the larvae of the horseradish leaf beetle (Phaedon cochleariae) or against the larvae of the green rice leafhopper
(Nephotettix cincticeps) gegen die Raupen der Kohlschabe (Plutella maculipennis). (Nephotettix cincticeps) against the caterpillars of the cockroach (Plutella maculipennis).
Die Wirkstoffe können in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-impräg- nierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymerenThe active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers
Stoffen. Substances.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents Agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkyl- naphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methyl isobutylketon oder Cyclo- hexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulf- oxid, sowie Wasser. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
Als feste Trägerstoffe kommen in Frage: The following are suitable as solid carriers:
z.B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen- Fettsäure-Ester, Polyoxyethylen-Fettalkohol -Ether, z.B. Alkylaryl-polyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Einweißhydrolysate; als Disper- giermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.  e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; suitable dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholi- pide. Weitere Additive können mineralische und vegetabile Öle sein. Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalo cyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden. Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue, and organic dyes, such as alizarin, azo and metal phthalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,5 und 90 %. Der erfindungsgemäße Wirkstoff kann in seinen handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit anderen Wirkstoffen, wie Insektiziden, Lockstoffen, Sterilantien, Bakteriziden, Akariziden, Nematiziden, Fungiziden, wachstumsregulierenden Stoffen oder Herbiziden vorliegen. Zu den Insektiziden zählen beispielsweise Phosphorsäureester, Carbamate, Carbonsäureester, chlorierte Kohlenwasserstoffe, Phenylharnstoffe, durch Mikroorganismen hergestellte Stoffe u.a. The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%. The active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
Besonders günstige Mischpartner sind z.B. die folgenden: Particularly cheap mixing partners are e.g. the following:
Fungizide: Fungicides:
2-Aminobutan; 2-Anilino-4-methyl-6-cyclopropyl-pyrimidin; 2',6'-Dibromo-2-methyM'-trifluoromethoxy^'-trifluoro-methyl-lAthiazol-S-carboxanilid; 2,6-Dichloro-N-(4-trifluoromethylbenzyl)-benzamid; (E)-2-Methoxyimino-N-methyl-2-(2- phenoxyphenyl)-acetamid; 8-Hydroxyquinolinsulfat; Methyl-(E)-2-{2-[6-(2-cyano- phenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylat; Methyl-(E)-methoximino- [alpha-(o-tolyloxy)-o-tolyl]acetat; 2-Phenylphenol (OPP), Aldimorph, Ampropylfos, Anilazin, Azaconazol,  2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyM'-trifluoromethoxy ^' - trifluoromethyl-l-thiazole-S-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyano-phenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,  Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, Chinomethionat (Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Cufraneb, Cymoxanil, Cyproconazole, Cyprofuram,  Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Dinocap, Diphenyl- amin, Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon,  Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, Epoxyconazole, Ethirimol, Etridiazol,  Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminium, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox, Guazatine, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyclox, Guazatine,
Hexachlorobenzol, Hexaconazol, Hymexazol,  Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion, Isoprothiolan, Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfernaphthenat, Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux-Mischung, Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,  Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol, Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Phthalid, Pimaricin, Piperalin, Polycarbamate, Polyoxin, Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,  Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB), Quintozen (PCNB),
Schwefel und Schwefel-Zubereitungen,  Sulfur and sulfur preparations,
Tebuconazol, Tecloftalam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen, Thio- phanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol,  Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamid, tricyclazole, tridemorph, triflorolizol, triflorolizol, triflorolizole,
Validarnycin A, Vinclozolin,  Validarnycin A, vinclozolin,
Zineb, Ziram.  Zineb, ziram.
Bakterizide: Bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.  Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide: Insecticides / acaricides / nematicides:
Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Abamectin, abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,
Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azin- phos M, Azocyclotin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifen- thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,
Butylpyridaben, Butyl pyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clo fentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin, 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clo fentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazi- non, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,  Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinone, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho- prophos, Etrimphos,  Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipro- nil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,  Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Fufionproxophon, Flufenproxionfon, Flufenproxionfon, Flufenproxionfon, Flufenproxionfon, Fufionproxophon, Fufionproxophon, Fufionproxophon, Fufionprox, Fufionprox, Fungionfoxx
HCH, Heptenophos, Hexaflumuron, Hexythiazox, HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin, Lamda-cyhalothrin, Lufenuron,  Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin, Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacrifos, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos,
Methami dophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Methami dophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,
Naled, NC 184, NI 25, Nitenpyram,  Naled, NC 184, NI 25, Nitenpyram,
Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,  Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Primiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Primiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quiproxifen
RH 5992,  RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,  Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiome- thon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb,  Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium
Vamidothion, XMC, Xylylcarb, YI 5301 / 5302, Zetamethrin. Herbizide: Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin. Herbicides:
beispielsweise Anilide, wie z.B. Diflufenican und Propanil; Aryl carbonsäuren, wie z.B. Dichlorpicoiinsäure, Dicamba und Picloram; Aryloxyalkansäuren, wie z.B. 2,4 D, 2,4 DB, 2,4 DP, Fluroxypyr, MCPA, MCPP und Triclopyr; Aryloxy-phenoxyalkansäureester, wie z.B. Diclofop-methyl, Fenoxaprop-ethyl, Fluazifop-butyl,e.g. anilides, e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichlorpicoic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxyalkanoic acid esters, e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl,
Haloxyfop-methyl und Quizalofop-ethyl; Azinone, wie z.B. Chloridazon und Norflurazon; Carbamate, wie z.B. Chlorpropham, Desmedipham, Phenmedipham und Propham; Chloracetanilide, wie z.B. Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Pretilachlor und Propachlor; Dinitroaniline, wie z.B. Oryzalin, Pendimethalin und Trifluralin; Diphenylether, wie z.B. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen und Oxyfluorfen; Harnstoffe, wie z.B. Chlortoluron, Diuron, Fluometuron, Isoproturon, Linuron und Methabenzthiazuron; Hydroxylamine, wie z.B. Alloxydim, Clethodim, Cycloxydim, Sethoxydim und Tralkoxydim; Imidazolinone, wie z.B. Imazethapyr, Imazamethabenz, Imazapyr und Imazaquin; Nitrile, wie z.B. Bromoxynil, Dichlobenil und Ioxynil; Oxyacetamide, wie z.B. Mefenacet; Sulfonylharnstoffe, wie z.B. Amidosulfuron, Bensulfuron-methyl, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Metsulfuronmethyl, Nicosulfuron, Primisulfuron, Pyrazosulfuron-ethyl, Thifensulfuron-methyl, Triasulfuron und Tribenuron-niethyl; Thiol carbamate, wie z.B. Butylate, Cycloate, Diallate, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb und Triallate;Haloxyfop-methyl and quizalofop-ethyl; Azinones, e.g. Chloridazon and norflurazon; Carbamates, e.g. Chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides, e.g. Alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines, e.g. Oryzalin, pendimethalin and trifluralin; Diphenyl ethers, e.g. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxyfluorfen; Ureas, e.g. Chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxylamines, e.g. Alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Imidazolinones, e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles, e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, e.g. Mefenacet; Sulfonylureas, e.g. Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuronmethyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-niethyl; Thiol carbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates;
Triazine, wie z.B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne und Terbutylazin; Triazinone, wie z.B. Hexazinon, Metamitron und Metribuzin; Sonstige, wie z.B. Aminotriazol, Benfuresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate und Tridiphane. Triazines, e.g. Atrazin, cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, such as Aminotriazole, Benfuresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
Der erfindungsgemäße Wirkstoff kann ferner in seinen handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit Synergisten vorliegen. Synergisten sind Verbindungen, durch die die Wirkung der Wirkstoffe gesteigert wird, ohne daß der zugesetzte Synergist selbst aktiv wirksam sein muß. The active ingredient according to the invention can also be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,0001 und 1 Gew.-% liegen. Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise. The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight. The application takes place in a customary manner adapted to the application forms.
Bei der Anwendung gegen Hygiene- und Vorratsschädlinge zeichnet sich der Wirkstoff durch eine hervorragende Residualwirkung auf Holz und Ton sowie durch eine gute Alkalistabilität auf gekalkten Unterlagen aus. When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor. The preparation and use of the active compounds according to the invention can be seen from the examples below.
Herstellungsbeispiele Manufacturing examples
Figure imgf000031_0001
Figure imgf000031_0001
Eine Lösung aus 3 g (7,7 mMol) N-[Morpholin-4-yl-(4-tert.-butylphenyl)-methyl]- 2,6-difluorbenzamid (vgl. Bsp. IIa-1) in 20 ml wasserfreiem Dichlormethan und 25 ml (25 mMol) Titan-IV-chlorid (1 -molare Lösung in Dichlormethan) wird bei Raumtemperatur im Autoklaven mit trockenem Chlorwasserstoff-Gas gesättigt. Danach wird bei ca. 0°C etwa 20 bis 30 Minuten lang Ethylen eingeleitet und anschließend 24 Stunden bei 70°C und ca. 14 bar Eigendruck gerührt. Das Reaktionsgemisch wird anschließend mit ca. 100 ml Eiswasser verrührt, bei 0°C mit Natronlauge alkalisch gestellt und mehrmals mit Dichlormethan extrahiert. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet und eingeengt. Der ölige Rückstand wird chromatographisch gereinigt.  A solution of 3 g (7.7 mmol) of N- [morpholin-4-yl- (4-tert-butylphenyl) methyl] -2,6-difluorobenzamide (see Example IIa-1) in 20 ml of anhydrous Dichloromethane and 25 ml (25 mmol) of titanium IV chloride (1 molar solution in dichloromethane) are saturated with dry hydrogen chloride gas in an autoclave at room temperature. Then ethylene is introduced at about 0 ° C. for about 20 to 30 minutes and then stirred for 24 hours at 70 ° C. and about 14 bar autogenous pressure. The reaction mixture is then stirred with about 100 ml of ice water, made alkaline at 0 ° C. with sodium hydroxide solution and extracted several times with dichloromethane. The combined organic phases are dried over magnesium sulfate and concentrated. The oily residue is purified by chromatography.
Man erhält 0,83 g (32,5 % der Theorie) 4-(4-tert.-Butylphenyl)-2-(2,6-difluorphenyl)-5,6-dihydro-4H-1,3-oxazin. 0.83 g (32.5% of theory) of 4- (4-tert-butylphenyl) -2- (2,6-difluorophenyl) -5,6-dihydro-4H-1,3-oxazine are obtained.
1H-NMR (ppm in CDCl3): 7.42-6.90 (m, 7H); 4.78 (m, 1H); 4.41-4.30 (m, 2H, 1H); 1.31 (s, 9H).
Figure imgf000032_0001
 1 H NMR (ppm in CDCl 3 ): 7.42-6.90 (m, 7H); 4.78 (m, 1H); 4.41-4.30 (m, 2H, 1H); 1.31 (s, 9H).
Figure imgf000032_0001
(ohne Zwischenisolierung der Verbindung (II))  (without intermediate insulation of connection (II))
3,5 g (20 mMol) 2-Chlor-6-fluorbenzoesäureamid werden in 40 ml Dichlormethan mit 3,4 g (21 mMol) 4-tert.-Butylbenzaldehyd und 2,1 g (24 mMol) Morpholin 183.5 g (20 mmol) of 2-chloro-6-fluorobenzoic acid amide are dissolved in 40 ml of dichloromethane with 3.4 g (21 mmol) of 4-tert-butylbenzaldehyde and 2.1 g (24 mmol) of morpholine 18
Stunden bei 50°C gerührt. Stirred at 50 ° C for hours.
Nach dem Abkühlen wird das Reaktionsgemisch mit 45 ml Titan-IV-chlorid (1- molare Lösung in Dichlormethan) versetzt und bei Raumtemperatur im Autoklaven mit trockenem Chlorwasserstoffgas gesättigt. Danach wird bei ca. 0°C etwa 20 bis 30 Minuten lang Ethylen eingeleitet und anschließend 24 Stunden bie 70°C und ca. 14 bar Eigendruck gerührt. Das Reaktionsgemisch wird mit ca. 150 ml Eiswasser verrührt, bei 0°C mit Natronlauge alkalisch gestellt und mehrmals mit Dichlormethan extrahiert. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet und eingeengt. Man erhält 1,38 g (30 % der Theorie) 4-(4-tert.-Butylphenyl)-2-(2-chlor-6-fluorphenyl)-5,6-dihydro-4H-1,3-oxazin mit einem logP-Weet von 4.71. After cooling, the reaction mixture is mixed with 45 ml of titanium IV chloride (1 molar solution in dichloromethane) and saturated with dry hydrogen chloride gas in an autoclave at room temperature. Then ethylene is introduced at about 0 ° C. for about 20 to 30 minutes and then stirred for 24 hours at 70 ° C. and about 14 bar internal pressure. The reaction mixture is stirred with about 150 ml of ice water, made alkaline at 0 ° C. with sodium hydroxide solution and extracted several times with dichloromethane. The combined organic phases are dried over magnesium sulfate and concentrated. 1.38 g (30% of theory) of 4- (4-tert-butylphenyl) -2- (2-chloro-6-fluorophenyl) -5,6-dihydro-4H-1,3-oxazine are obtained with a logP-Weet from 4.71.
Gemäß den Beispielen 1 und 2 sowie entsprechend den allgemeinen Verfahrensangaben können die folgenden Verbindungen der allgemeinen Formel (I) erhalten werden: According to Examples 1 and 2 and in accordance with the general procedure, the following compounds of the general formula (I) can be obtained:
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Zu einer Lösung von 12,8 g (81,5 m Mol) 2,6-Difluorbenzoesäureamid in 100 ml wasserfreiem Methanol gibt man 13,6 g (84 m Mol) 4-tert.-Butylbenzaldehyd und 8,5 g (97,7 m Mol) Morpholin und rührt das Reaktionsgemisch 24 Stunden bei ca. 40 bis 50°C. Anschließend wird mit ca. 100 ml Eiswasser verrührt, der Niederschlag abgesaugt, mit Wasser gewaschen und getrocknet.  To a solution of 12.8 g (81.5 m mol) of 2,6-difluorobenzoic acid amide in 100 ml of anhydrous methanol are added 13.6 g (84 m mol) of 4-tert-butylbenzaldehyde and 8.5 g (97, 7 m mol) of morpholine and the reaction mixture is stirred at about 40 to 50 ° C. for 24 hours. The mixture is then stirred with about 100 ml of ice water, the precipitate is filtered off with suction, washed with water and dried.
Man erhält 21 g (67 % der Theorie) N-[Morpholin-4-yl-(4-tert.-butylphenyl)- methyl]-2,6-difluorbenzamid vom Schmelzpunkt 199-200°C. 21 g (67% of theory) of N- [morpholin-4-yl- (4-tert-butylphenyl) methyl] -2,6-difluorobenzamide with a melting point of 199-200 ° C. are obtained.
Figure imgf000065_0001
Figure imgf000065_0001
3,5 g (20 m Mol) 2-Chlor-6-fluorbenzoesäureamid werden in 30 ml Methanol mit 3,4 g (21 m Mol) 4-tert.-Butyl-benzaldehyd und 2,1 g (24,1 m Mol) Morpholin 18 Stunden bei 50°C gerührt. Nach dem Abkühlen wird das Reaktionsgemisch mit 100 ml Eiswasser verrührt, der Niederschlag abgesaugt, mit Wasser gewaschen und getrocknet.  3.5 g (20 moles) of 2-chloro-6-fluorobenzoic acid amide are mixed in 30 ml of methanol with 3.4 g (21 moles) of 4-tert-butyl-benzaldehyde and 2.1 g (24.1 moles ) Morpholine stirred at 50 ° C for 18 hours. After cooling, the reaction mixture is stirred with 100 ml of ice water, the precipitate is filtered off, washed with water and dried.
Man erhält 6,3 g (77,4 % der Theorie) N-[Morpholin-4-yl-(4-tert.-butylphenyl)- methyl]-2-chlor-6-fluor-benzamid vom Schmelzpunkt 180-181°C. Gemäß den Beispielen (Ha- 1 ) und (IIa-2) sowie entsprechend den allgemeinen6.3 g (77.4% of theory) of N- [morpholin-4-yl- (4-tert-butylphenyl) methyl] -2-chloro-6-fluoro-benzamide with a melting point of 180-181 ° are obtained C. According to examples (Ha-1) and (IIa-2) and according to the general
Verfahrensangaben werden die folgenden Ausgangsprodukte der Formel (Ila) erhalten: The following starting products of the formula (Ila) are obtained:
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Anwendungsbeispiele Beispiel A Application examples Example A
Plutella-Test Plutella test
Lösungsmittel: 7 Gewichtsteile Dimethylformamid Solvent: 7 parts by weight of dimethylformamide
Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration. Kohlblätter (Brassica oleracea) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Raupen der Kohlschabe (Plutella maculipennis) besetzt, solange die Blätter noch feucht sind. To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cabbage cockroach (Plutella maculipennis) while the leaves are still moist.
Nach der gewünschten Zeit wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, daß alle Raupen abgetötet wurden; 0 % bedeutet, daß keine Raupen abgetötet wurden. After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
In diesem Test bewirkte die Verbindung gemäß Beispiel IIa-5 bei einer beispielhaften Wirkstoffkonzentration von 0J % nach 7 Tagen eine Abtötung von 100 %. In this test, the compound according to Example IIa-5, with an exemplary active compound concentration of 0J%, caused 100% killing after 7 days.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Verbindungen der Formel (I) 1. Process for the preparation of compounds of formula (I)
Figure imgf000070_0001
Figure imgf000070_0001
in welcher A für substituiertes Phenyl oder für jeweils gegebenenfalls substituiertes Naphthyl, Pyridyl, Thienyl oder Pyrazolyl steht und  in which A stands for substituted phenyl or for optionally substituted naphthyl, pyridyl, thienyl or pyrazolyl and
B für Wasserstoff, Alkyl, Alkoxyalkyl, Alkylthioalkyl, Halogenalkyl,B for hydrogen, alkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl,
Alkenyl, gegebenenfalls substituiertes Cycloalkyl oder jeweils gegebenenfalls substituiertes Phenyl, Phenylalkyl, Phenylalkenyl, Phenoxyalkyl, Phenylthioalkyl, Pyridyl, 2- oder 3-Pyrrolyl steht, dadurch gekennzeichnet, daß wenn man Amid-Derivate der Formel (II) Alkenyl, optionally substituted cycloalkyl or in each case optionally substituted phenyl, phenylalkyl, phenylalkenyl, phenoxyalkyl, phenylthioalkyl, pyridyl, 2- or 3-pyrrolyl, characterized in that if amide derivatives of the formula (II)
Figure imgf000070_0002
Figure imgf000070_0002
in welcher  in which
A und B die oben angegebene Bedeutung haben und R1 und R2 gleich oder verschieden sind und jeweils für Alkyl stehen oder A and B have the meaning given above and R 1 and R 2 are identical or different and are each alkyl or
gemeinsam mit dem N-Atom, an das sie gebunden sind, für einen gegebenenfalls substituierten Heterocyclus stehen, mit Ethylen in Gegenwart von Chlorwasserstoff-Gas und eines Katalysators, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt. together with the N atom to which they are attached represent an optionally substituted heterocycle, with ethylene in the presence of hydrogen chloride gas and a catalyst, if appropriate in the presence of a diluent.
2. Verbindungen der Formel (Ila) 2. Compounds of the formula (Ila)
Figure imgf000071_0001
Figure imgf000071_0001
in welcher  in which
A, R1 und R2 die in Anspruch 1 angegebene Bedeutung haben und B2 die in Anspruch 1 für B angegebene Bedeutung mit Ausnahme von Wasserstoff hat. A, R 1 and R 2 have the meaning given in claim 1 and B 2 has the meaning given for B in claim 1 with the exception of hydrogen.
3. Verbindungen der Formel (Ib) 3. Compounds of formula (Ib)
Figure imgf000071_0002
Figure imgf000071_0002
in welcher A die in Anspruch 1 angegebene Bedeutung hat und  in which A has the meaning given in claim 1 and
D für jeweils gegebenenfalls substituiertes 2- oder 3-Pyrrolyl oder für durch CHO, Cyano, Carboxyl, Polyalkoxyalkyl oder Alkoxycarbo- nyl substituiertes Phenyl steht. D stands for optionally substituted 2- or 3-pyrrolyl or for phenyl substituted by CHO, cyano, carboxyl, polyalkoxyalkyl or alkoxycarbonyl.
4. Schädlingsbekämpfungsmittel, gekennzeichnet durch einen Gehalt an min- destens einer Verbindung der Formel (Ib) gemäß Anspruch 3. 4. pesticides, characterized by a content of at least one compound of the formula (Ib) according to claim 3.
5. Verwendung von Verbindungen der Formel (Ib) gemäß Anspruch 3 zur Bekämpfung von Schädlingen. 5. Use of compounds of formula (Ib) according to claim 3 for combating pests.
6. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daß man Verbindungen der Formel (Ib) gemäß Anspruch 3 auf Schädlinge und/oder ihren Lebensraum einwirken läßt. 6. A method for controlling pests, characterized in that compounds of the formula (Ib) according to Claim 3 are allowed to act on pests and / or their habitat.
7. Verfahren zur Herstellung von Schädlingsbekämpfungsmitteln, dadurch gekennzeichnet, daß man Verbindungen der Formel (Ib) gemäß Anspruch 3 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt. 7. A process for the preparation of pesticides, characterized in that compounds of the formula (Ib) according to Claim 3 are mixed with extenders and / or surface-active agents.
8. Verwendung von Verbindungen der Formel (Ib) gemäß Anspruch 3 zur Herstellung von Schädlingsbekämpfungsmitteln. 8. Use of compounds of formula (Ib) according to claim 3 for the preparation of pesticides.
PCT/EP1996/001954 1995-05-22 1996-05-09 Process for producing 5,6-dihydro-1,3-oxazines WO1996037484A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR9609218A BR9609218A (en) 1995-05-22 1996-05-09 Process for the preparation of 5,6-dihydro-1,3-oxazines
EP96914186A EP0827499B1 (en) 1995-05-22 1996-05-09 Process for producing 5,6-dihydro-1,3-oxazines
AU57640/96A AU5764096A (en) 1995-05-22 1996-05-09 Process for producing 5,6-dihydro-1,3-oxazines
JP8535306A JPH11505261A (en) 1995-05-22 1996-05-09 Method for producing 5,6-dihydro-1,3-oxazine
US08/930,051 US5892030A (en) 1995-05-22 1996-05-09 Process for producing 5,6-dihydro-1,3-oxazines
DE59611076T DE59611076D1 (en) 1995-05-22 1996-05-09 METHOD FOR PRODUCING 5,6-DIHYDRO-1,3-OXAZINE

Applications Claiming Priority (2)

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DE19518681.8 1995-05-22
DE19518681A DE19518681A1 (en) 1995-05-22 1995-05-22 Process for the preparation of 5,6-dihydro-1,3-oxazines

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WO2008026658A1 (en) 2006-09-01 2008-03-06 Otsuka Chemical Co., Ltd. N-pyridylpiperidine compound, method for producing the same, and pest control agent

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CA2839703A1 (en) 2011-06-24 2012-12-27 Amgen Inc. Trpm8 antagonists and their use in treatments
PE20140868A1 (en) 2011-06-24 2014-07-18 Amgen Inc TRPM8 ANTAGONISTS AND THEIR USE IN TREATMENTS
US8952009B2 (en) 2012-08-06 2015-02-10 Amgen Inc. Chroman derivatives as TRPM8 inhibitors
MX2020013099A (en) 2013-06-27 2022-07-26 Pfizer Heteroaromatic compounds and their use as dopamine d1 ligands.
EP3860993B1 (en) * 2018-10-06 2022-08-10 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives

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DE1545671A1 (en) * 1965-05-05 1969-08-07 Huels Chemische Werke Ag Process for the preparation of 4H-5,6-dihydro-1,3-oxazines
DE1670475A1 (en) * 1967-09-29 1971-01-28 Huels Chemische Werke Ag Process for the preparation of 4H-5,6-dihydro-1,3-oxazines substituted in the 4-position
DE2049160A1 (en) * 1970-10-07 1972-04-13 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen 4,4-dimethyl-5,6-dihydro-1,3-oxazines prodn - by reacting corresp nitrile with 3-methylbutenol
EP0394850A1 (en) * 1989-04-28 1990-10-31 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of 5,6-dihydro-4H-1,3-oxazines
WO1993022296A1 (en) * 1992-05-04 1993-11-11 Henkel Kommanditgesellschaft Auf Aktien Process for producing substituted oxazolines and/or oxazines

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DE1545671A1 (en) * 1965-05-05 1969-08-07 Huels Chemische Werke Ag Process for the preparation of 4H-5,6-dihydro-1,3-oxazines
DE1670475A1 (en) * 1967-09-29 1971-01-28 Huels Chemische Werke Ag Process for the preparation of 4H-5,6-dihydro-1,3-oxazines substituted in the 4-position
DE2049160A1 (en) * 1970-10-07 1972-04-13 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen 4,4-dimethyl-5,6-dihydro-1,3-oxazines prodn - by reacting corresp nitrile with 3-methylbutenol
EP0394850A1 (en) * 1989-04-28 1990-10-31 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of 5,6-dihydro-4H-1,3-oxazines
WO1993022296A1 (en) * 1992-05-04 1993-11-11 Henkel Kommanditgesellschaft Auf Aktien Process for producing substituted oxazolines and/or oxazines

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008026658A1 (en) 2006-09-01 2008-03-06 Otsuka Chemical Co., Ltd. N-pyridylpiperidine compound, method for producing the same, and pest control agent
US7994094B2 (en) 2006-09-01 2011-08-09 Otsuka Agritechno Co., Ltd. N-pyridylpiperidine compound, method for producing the same, and pest control agent

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CN1191532A (en) 1998-08-26
HUP9801229A2 (en) 1998-09-28
KR19990014864A (en) 1999-02-25
US5892030A (en) 1999-04-06
CN1071322C (en) 2001-09-19
BR9609218A (en) 1999-02-17
JPH11505261A (en) 1999-05-18
EP0827499A1 (en) 1998-03-11
TW312692B (en) 1997-08-11
DE59611076D1 (en) 2004-10-07
ES2229266T3 (en) 2005-04-16
DE19518681A1 (en) 1996-11-28
EP0827499B1 (en) 2004-09-01
AU5764096A (en) 1996-12-11
KR100420159B1 (en) 2004-05-31

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